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High Li and Mg conductivity in a Cu-azolate metal-organic framework Elise M. Miner, Sarah S. Park, and Mircea Dinca J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13418 • Publication Date (Web): 18 Feb 2019 Downloaded from http://pubs.acs.org on February 18, 2019
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Journal of the American Chemical Society
High Li+ and Mg2+ conductivity in a Cu‐azolate metal‐organic frame‐ work Elise M. Miner, Sarah S. Park, and Mircea Dincă* Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachu‐ setts 02139, United States Supporting Information ABSTRACT: A Cu‐azolate metal‐organic framework uptakes stoichiometric loadings of Group 1 and 2 metal halides, demonstrat‐ ing efficient reversible release and reincorporation of immobilized anions within the framework. Ion pairing interactions lead to anion‐dependent Li+ and Mg2+ transport in Cu4(ttpm)2∙0.6CuCl2, whose high surface area affords a high density of uniformly dis‐ tributed mobile metal cations and halide binding sites. The ability to systematically tune the ionic conductivity yields a solid electrolyte with a Mg2+ ion conductivity rivaling the best materials reported to date. This MOF is one of the first in a promising class of frameworks that introduces the opportunity to control the identity, geometry, and distribution of the cation hopping sites, offering a versatile template for application‐directed design of solid electrolytes.
INTRODUCTION Since the emergence of the first rechargeable galvanic cell in 1860,1 rechargeable batteries have become an enabling tech‐ nology for a range of critical processes in modern life. Alt‐ hough old in a sense, rechargeable battery technologies repre‐ sent an important field of modern research, spurred by the scale and variety of applications stemming from an inevitable transition to renewable and clean energy technologies. Among the various possible technologies, metal and metal‐ion batteries are particularly versatile in serving a range of appli‐ cations especially in consumer electronics, where they offer a combination of high volumetric capacity and ~1000‐cycle life‐ time that is well suited for such devices.2 However, despite sig‐ nificant advances there is much room for improvement in ef‐ ficiency, lifetime, and safety of metal and metal‐ion batteries. All these could be improved by transitioning from liquid elec‐ trolytes, the current industry standard, to solid ion conduc‐ tors. Liquid electrolytes exhibit relatively narrow potential stability windows, cation transference numbers of
